Processes for the preparation of 1,4-diaryl-2-fluoro-1,3-butadiene and 1,4-diaryl-2-fluoro 2 butene compounds

ABSTRACT

The present invention provides an improved process for the preparation of 1,4-diaryl-2-fluoro-1,3-butadiene compounds of the structural formula I                    
     In addition, the present invention provides an improved process for the preparation of 1,4-diaryl-2-fluoro-2-butadiene compounds of the structural formula IV

This application is a 371 of PCT/US99/26387, filed Nov. 9, 1999, now WO00/29363, which is a CIP of US 09/192,687 filed Nov. 5 1998, nowabandoned.

BACKGROUND OF THE INVENTION

1,4-Diaryl-2-fluoro-1,3-butadiene compounds, methods for theirpreparation, and their use as intermediates in the preparation of1,4-diaryl-2-fluoro-2-butene insecticidal and acaricidal agents aredescribed in EP 811593-A1. The methods described in EP 811593-A1 for thepreparation of 1,4-diaryl-2-fluoro-1,3-butadiene compounds require theuse of phosphonium halide compounds. However, these methods are notentirely satisfactory because the required phosphonium halide compoundsare relatively expensive and produce undesirable by-products which aredifficult to remove from the 1,4-diaryl-2-fluoro-1,3-butadienecompounds. Accordingly, a need exists in the art for an improved processfor the preparation of 1,4-diaryl-2-fluoro-1,3-butadiene compounds whichavoids the use of phosphonium halide compounds.

It is, therefore, an object of the present invention to provide animproved process for the preparation of1,4-diaryl-2-fluoro-1,3-butadiene compounds which avoids the use ofphosphonium halide compounds.

It is also an object of the present invention to provide an improvedprocess for the preparation of 1,4-diaryl-2-fluoro-2-butene compounds.

Other objects and advantages of the present invention will be apparentto those skilled in the art from the description below and the appendedclaims.

SUMMARY OF THE INVENTION

The present invention provides a new process for the preparation of1,4-diaryl-2-fluoro-1,3-butadiene compounds of the structural formula I

wherein

R is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl or C₃-C₆halocycloalkyl;

Ar is phenyl optionally substituted with any combination of from one tothree halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups,

1- or 2-naphthyl optionally substituted with any combination of from oneto three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl C₁-C₄alkoxy orC₁-C₄haloalkoxy groups, or

a 5- or 6-membered heteroaromatic ring optionally substituted with anycombination of from one to three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy or C₁-C₄haloalkoxy groups; and

Ar₁ is phenoxyphenyl optionally substituted with any combination of fromone to six halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups,

phenyl optionally substituted with any combination of from one to fivehalogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, or C₁-C₄haloalkoxygroups,

biphenyl optionally substituted with any combination of from one to fivehalogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxygroups,

phenoxypyridyl optionally substituted with any combination of from oneto five halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups,

benzylpyridyl optionally substituted with any combination of from one tofive halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxygroups,

benzylphenyl optionally substituted with any combination of from one tofive halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxygroups,

benzoylphenyl optionally substituted with any combination of from one tofive halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxygroups,

1- or 2-naphthyl optionally substituted with any combination of from oneto three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups, or

a 5- or 6-membered heteroaromatic ring optionally substituted with anycombination of from one to three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy or C₁-C₄haloalkoxy groups,

which process comprises reacting an arylmethanesulfonyl fluoride orarylmethanephosphonate compound of the structural formula II

Ar₁CH₂Y  (II)

wherein Y is SO₂F or P(O) (OR₁)₂, R₁ is C₁-C₄alkyl, and

Ar₁ is as hereinbefore defined with a 3-aryl-2-fluoropropenal compoundof the structural formula III

wherein R and Ar are as hereinbefore defined in the presence of a base.

The present invention further provides a new process for the preparationof 1,4-diaryl-2-fluoro-2-butene compounds of the structural formula IV

wherein

R is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl or C₃-C₄halocycloalkyl;

Ar is phenyl optionally substituted with any combination of from one tothree halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups,

1- or 2-naphthyl optionally substituted with any combination of from oneto three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl C₁-C₄alkoxy orC₁-C₄haloalkoxy groups, or

a 5- or 6-membered heteroaromatic ring optionally substituted with anycombination of from one to three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy or C₁-C₄haloalkoxy groups; and

Ar₁ is phenoxyphenyl optionally substituted with any combination of fromone to six halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups,

phenyl optionally substituted with any combination of from one to fivehalogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, or C₁-C₄haloalkoxygroups,

biphenyl optionally substituted with any combination of from one to fivehalogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxygroups,

phenoxypyridyl optionally substituted with any combination of from oneto five halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups,

benzylpyridyl optionally substituted with any combination of from one tofive halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxygroups,

benzylphenyl optionally substituted with any combination of from one tofive halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxygroups,

benzoylphenyl optionally substituted with any combination of from one tofive halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxygroups,

1- or 2-naphthyl optionally substituted with any combination of from oneto three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups, or

a 5- or 6-membered heteroaromatic ring optionally substituted with anycombination of from one to three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy or C₁-C₄haloalkoxy groups,

which process comprises the steps of:

(a) reacting an arylmethanesulfonyl fluoride or arylmethanephosphonatecompound of the structural formula II

Ar₁CH₂Y  (II)

wherein Y is SO₂F or P(O) (OR₁)₂, R₁ is C₁-C₄alkyl, and

Ar₁ is as described above with a 3-aryl-2-fluoropropenal compound of thestructural formula III

wherein R and Ar are as described above in the presence of a base toform a 1,4-diaryl-2-fluoro-1,3-butadiene compound of the structuralformula I

(b) reacting the 1,4-diaryl-2-fluoro-1,3-butadiene compound with: (1) analkaline earth metal in the presence of a protic solvent, or (2) analkali metal in the presence of an aprotic solvent.

DETAILED DESCRIPTION OF THE INVENTION

In a preferred embodiment of the present invention, the1,4-diaryl-2-fluoro-1,3-butadiene compounds of formula I are prepared byreacting an arylmethanesulfonyl fluoride or arylmethanephosphonatecompound of formula II with a 3-aryl-2-fluoropropenal compound offormula III and a base, preferably at a temperature ranging from about−78° C. to 150° C., more preferably from about −20° C. to about 100° C.,in the presence of a solvent.

In another preferred embodiment of the present invention, the1,4-diaryl-2-fluoro-2-butene compounds of formula IV are prepared byreacting an arylmethanesulfonyl fluoride or arylmethanephosphonatecompound of formula II with a 3-aryl-2-fluoropropenal compound offormula III and a base, preferably at a temperature ranging from about−78° C. to about 150° C., more preferably from about −20° C. to about100° C., in the presence of a solvent to form a1,4-diaryl-2-fluoro-1,3-butadiene compound of formula I, and reactingthe formula I butadiene compound with an alkaline earth metal in thepresence of a protic solvent.

Most advantageously, the present invention provides a process for thepreparation of 1,4-diaryl-2-fluoro-1,3-butadiene compounds which avoidsthe use of phosphonium halide compounds.

The product formula I and IV compounds may be isolated by diluting thereaction mixture with water and extracting the product with a suitableextraction solvent. In the isolation procedure, conventional extractionsolvents such as diethyl ether, ethyl acetate, toluene, methylenechloride, and the like, and mixtures thereof may be utilized.

Bases suitable for use in the present invention include, but are notlimited to, alkali metal hydrides such as sodium hydride and the like;alkali metal C₁-C₆alkoxides such as sodium methoxide and the like;alkali metal hydroxides such as potassium hydroxide, sodium hydroxideand the like; alkali metal carbonates such as potassium carbonate,sodium carbonate and the like; alkaline earth metal hydroxides such ascalcium hydroxide and the like; alkaline earth metal carbonates such ascalcium carbonate and the like; lithium bases such as alkyllithiumsincluding n-butyllithium, sec-butyllithium, tert-butyllithium,methyllithium and the like, lithium dialkylamides including lithiumdiiso-propylamide and the like, and lithium cyclicamides includinglithium tetramethylpiperidine and the like; and tri(C₁-C₆alkyl)aminessuch as trimethylamine, triethylamine, tripropylamine, tributylamine,diisopropylethylamine and the like. Preferred bases include alkali metalC₁-C₆alkoxides and alkali metal carbonates.

Solvents useful in the preparation of the formula I compounds of thisinvention include, but are not limited to, carboxylic acid amides suchas N,N-dimethylformamide, N,N-dimethylacetamide and the like; etherssuch as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane andthe like; nitrites such as acetonitrile, propionitrile and the like;dialkyl sulfoxides such as dimethyl sulfoxide and the like; aromatichydrocarbons such as toluene, benzene, xylenes, mesitylene and the like;and C₁-C₆alcohols such as methanol, ethanol, isopropanol, propanol andthe like; and mixtures thereof. Preferred solvents includes ethers andnitrites.

Protic solvents suitable for use in this invention include, but are notlimited to, C₁-C₆alcohols such as methanol, ethanol and the like.Preferred protic solvents include methanol and ethanol.

Aprotic solvents include, but are not limited to, ammonia; and etherssuch as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane andthe like.

Alkaline earth metals suitable for use in the preparation of the formulaIV compounds include, but are not limited to, magnesium and calcium withmagnesium being preferred. Alkali metals include, but are not limitedto, lithium, sodium and potassium.

In another preferred embodiment of the present invention, thearylmethanesulfonyl fluoride or arylmethanephosphonate compound isreacted with the 3-aryl-2-fluoropropenal compound and the base in thepresence of a catalytically effective amount of a phase transfercatalyst. Phase transfer catalysts suitable for use in this inventioninclude, but are not limited to, crown ethers such as 18-crown-6,15-crown-5, 12-crown-4 and the like; quaternary ammonium salts such astricaprylymethylammonium chloride and the like; and cryptands such as1,4,10-trioxa-7,13-diazacyclo-pentadecane,4,7,13,18-tetraoxa-1,10-diazabicyclo-[8.5.5]eicosane,4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane,5,6-benzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane andthe like.

In a preferred process of this invention, R₁ is an ethyl group when anarylmethanephosphonate compound is used to prepare the formula Icompounds.

Preferred formula I and II compounds which may be prepared by theprocesses of this invention are those wherein

R is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl or C₃-C₆halocycloalkyl;

Ar is phenyl optionally substituted with any combination of from one tothree halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups; and

Ar₁ is 3-phenoxyphenyl optionally substituted with any combination offrom one to six halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups,

3-biphenyl optionally substituted with any combination of from one tofive halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxygroups, or

3-benzylphenyl optionally substituted with any combination of from oneto five halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups.

Highly preferred 1,4-diaryl-2-fluoro-1,3-butadiene and1,4-diaryl-2-fluoro-2-butene compounds which may be prepared by theprocesses of this invention are those wherein

R is isopropyl or cyclopropyl;

Ar is phenyl optionally substituted with any combination of from one tothree halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups; and

Ar₁ is 3-phenoxyphenyl optionally substituted with any combination offrom one to six halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy groups.

The present invention is especially useful for the preparation of

1-(p-chlorophenyl)-1-cyclopropyl-2-fluoro-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadiene;and

1-[1-(p-chlorophenyl)-2-fluoro-4-(4-fluoro-3-phenoxyphenyl)-2-butenyl]cyclopropane.

In formulas I and IV above, the 5- and 6-membered heteroaromatic ringmay suitably be a ring containing one to four heteroatoms selected fromN, O and S, wherein the heteroatoms may be the same or different, e.g.the rings include, but are not limited to, pyridyl, pyrazolyl,imidazolyl, triazolyl, isoxazolyl, tetrazolyl, pyrazinyl, pyridazinyl,triazinyl, furanyl, thienyl and thiazolyl rings each optionallysubstituted a as described in formulas I and IV above.

Exemplary of “halogen” as used herein are fluorine, chlorine, bromineand iodine. The terms “C₁-C₄haloalkyl”, “C₃-C₆halocycloalkyl” and“C₁-C₄haloalkoxy” are defined as a C₁-C₄alkyl group, a C₃-C₆cycloalkylgroup and a C₁-C₄alkoxy group substituted with one or more halogenatoms, respectively, wherein the halogen atoms may be the same ordifferent.

When used herein as a group or part of a group the term “alkyl” includesstraight or branched chain alkyl groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, s-butyl and t-butyl. When used herein as agroup or part of a group the term “cycloalkyl” incudes cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl.

Groups containing two or more rings, such as biphenyl, phenoxypyridyland benzylphenyl, which may be substituted, may be substituted on eitherring unless otherwise specified herein.

Starting arylmethanesulfonyl fluoride compounds of formula II wherein Yis SO₂F may be prepared, as shown in Flow Diagram I, by reacting anarylmethanebromide compound of the structural formula V with sodiumsulfite to form a sodium arylmethanesulfonate compound of the structuralformula VI, reacting the formula VI sulfonate compound with phosphorouspentachloride to form an arylmethanesulfonyl chloride compound of thestructural formula VII, and reacting the sulfonyl chloride compound withpotasium fluoride.

Starting arylmethanephosphonate compounds of formula II wherein Y isP(O) (OR₁)₂ may be prepared as shown in Flow Diagram II, by reacting anarylmethanebromide compound of the structural formula V with atri-(C₁-C₄alkyl)phosphite compound of the structural formula VIII.

3-Aryl-2-fluoropropenal compounds of structural formula III may beprepared according to the procedures described in EP 811593-A1.

In order to facilitate a further understanding of this invention, thefollowing examples are presented primarily for the purpose ofillustrating more specific details thereof. The scope of the inventionshould not be deemed limited by the examples but encompasses the entiresubject matter defined in the claims.

EXAMPLE 1 Preparation of (4-Fluoro-3-phenoxyphenyl)methane-sulfonylFluoride

Step 1

A mixture of α-bromo-4-fluoro-3-phenoxytoluene (4.86 g, 17.3 mmol) andsodium sulfite (2.39 g, 19 mmol) in 50% aqueous methanol (20 ml) isheated at reflux for 5 hours and cooled to room temperature. Theresultant colorless solid is collected by filtration and washed withchilled 50% aqueous methanol and methanol to obtain 3.4 g of sodium(4-fluoro-3-phenoxyphenyl)methanesulfonate. Another 1.8 g of product isrecovered from the mother liquors.

Step 2

The sodium sulfonate obtained in step 1 is mixed with phosphorouspentachloride at room temperature for two days. An ice-water mixture isadded and the aqueous solution is extracted with methylene chloride. Theorganic extract is washed with water, dried over anhydrous sodiumsulfate, and concentrated in vacuo to obtain(4-fluoro-3-phenoxyphenyl)methanesulfonyl chloride as a syrup (2.05 g).

Step 3

The sulfonyl chloride obtained in step 2 (2.0 g, 6.65 mmol) is dilutedwith acetonitrile (20 ml). The resultant solution is treated withpotassium fluoride (1.93 g, 33.25 mmol) and tetrabutylamonium fluoride(0.208 g, 0.66 mmol), stirred at room temperature for one day, pouredinto water, and extracted with ethyl acetate. The organic extract iswashed with water, dried over anhydrous sodium sulfate, and concentratedin vacuo to obtain a residue. Flash chromatography of the residue onsilica gel eluting with 15:85 ethyl acetate/hexanes gives(4-fluoro-3-phenoxyphenyl)methanesulfonyl fluoride (0.81 g, mp59.5-61.5° C.) which is identified by ¹H and ¹⁹F NMR spectral analyses.

EXAMPLE 2 Preparation of1-(p-Chlorophenyl)-1-cyclopropyl-2-fluoro-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadiene

A mixture of p-chloro-β-cyclopropyl-α-fluoro-cinnamaldehyde (224.6 mg, 1mmol), (4-fluoro-3-phenoxyphenyl)methanesulfonyl fluoride (312.7 mg, 1.1mmol), potassium carbonate (552.8 mg, 4 mmol), and 18-crown-6 (13.2 mg,0.05 mmol) in acetonitrile is stirred at room temperature overnight,quenched with water, and extracted with ethyl acetate. The organicextract is washed with water, dried over anhydrous sodium sulfate, andconcentrated in vacuo to give the title product (380 mg, 94% pure by GCanalysis, 93% yield) which is identified by ¹H and ¹⁹F NMR spectralanalyses.

EXAMPLE 3 Preparation of Diethyl (4-Fluoro-3-phenoxybenzyl)-phosphonate

A mixture of 4-fluoro-3-phenoxybenzyl bromide (28.1 g, 100 mmol) andtriethyl phosphite (18.27 g, 110 mmol) is heated at 90° C. for 30minutes while allowing some low boiling materials to distill off. Theresultant mixture is heated at 140° C. for 3.5 hours and distilled at120° C./2 mmHg to give the title product as a syrup (32.1 g, 95% yield)which is identified by ¹H and ¹⁹F NMR spectral analyses.

EXAMPLE 4 Preparation of1-(p-Chlorophenyl)-1-cyclopropyl-2-fluoro-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadiene

A stirred solution of diethyl (4-fluoro-3-phenoxybenzyl)phosphonate(2.64 g, 7.8 mmol) and p-chloro-β-cyclopropyl-α-fluorocinnamaldehyde(1.35 g, 6 mmol) in tetrahydrofuran (20 ml) is treated with sodiummethoxide (562 mg, 9.36 mmol) at 0° C., stirred at room temperatureovernight, quenched with 2 N aqueous hydrochloric acid, and extractedwith ethyl acetate. The organic extract is washed sequentially withwater, 2 N aqueous hydrochloric acid and water, dried over anhydroussodium sulfate, and concentrated in vacuo to obtain a residue. Flashchromatography of the residue on silica gel eluting with 1:9 ethylacetate/hexanes gives the title product as a syrup (2.15 g, 87.7% yield)which is identified by ¹H and ¹⁹F NMR spectral analyses.

What is claimed is:
 1. A process for the preparation of a1,4-diaryl-2-fluoro-1,3-butadiene compound of the structural formula I

wherein R is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl orC₃-C₆-halocycloalkyl; Ar is phenyl optionally substituted with anycombination of from one to three halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy or C₁-C₄-haloalkoxy groups, 1- or 2-naphthyl optionallysubstituted with any combination of from one to three halogen,C₁-C₄-alkyl, C₁-C₄haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy groups;and Ar₁ is phenoxyphenyl optionally substituted with any combination offrom one to six halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy groups, phenyl optionally substituted with anycombination of from one to five halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy, or C₁-C₄-haloalkoxy groups, biphenyl optionallysubstituted with any combination of from one to five halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy groups,benzylphenyl optionally substituted with any combination of from one tofive halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy groups, benzoylphenyl optionally substituted with anycombination of from one to five halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy or C₁-C₄-haloalkoxy groups, or 1- or 2-naphthyl optionallysubstituted with any combination of from one to three halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy groups,which process comprises reacting an arylmethanesulfonyl fluoride orarylmethanephosphonate compound of the structural formula II Ar₁CH₂Y  (II) wherein Y is SO₂F or P(O)(OR₁)₂, R₁ is C₁-C₄-alkyl, andAr₁ is as described above with a 3-aryl-2-fluoropropenal compound of thestructural formula III

wherein R and Ar are as hereinbefore defined, in the presence of a base.2. The process according to claim 1 wherein the base is selected fromthe group consisting of an alkali metal hydride, an alkali metalC₁-C₆-alkoxide, an alkali-metal hydroxide, an alkali metal carbonate, analkaline earth metal hydroxide, an alkaline earth metal carbonate, alithium base and a tri(C₁-C₆-alkyl)amine.
 3. The process according toclaim 2 wherein the base is selected from the group consisting of analkali metal C₁-C₆-alkoxide and an alkali metal carbonate.
 4. Theprocess according to claim 1 wherein the arylmethanesulfonyl fluoride orarylmethanephosphonate compound is reacted with the3-aryl-2-fluoropropenal compound and the base in the presence of asolvent.
 5. The process according to claim 4 wherein the solvent isselected from the group consisting of a carboxylic acid amide, an ether,a nitrile, a dialkyl sulfoxide, an aromatic hydrocarbon and aC₁-C₆-alcohol and mixtures thereof.
 6. The process according to claim 5wherein the solvent is selected from the group consisting of an etherand a nitrile.
 7. The process according to claim 1 wherein thearylmethanesulfonyl fluoride or arylmethanephosphonate compound isreacted with the 3-aryl-2-fluoropropenal compound and the base at atemperature ranging from about −78° C. to 150° C.
 8. The processaccording to claim 7 wherein the temperature range is from about −20° C.to 100° C.
 9. The process according to claim 1 wherein R is C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl or C₃-C₆-halocycloalkyl; Ar is phenyloptionally substituted with any combination of from one to threehalogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxygroups; Ar₁ is 3-phenoxyphenyl optionally substituted with anycombination of from one to six halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy or C₁-C₄-haloalkoxy groups, 3-biphenyl optionallysubstituted with any combination of from one to five halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy groups,or 3-benzylphenyl optionally substituted with any combination of fromone to five halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy groups; Y is SO₂F or P(O)(OR₂)₂; and R₁ is C₁-C₄-alkyl.10. The process according to claim 9 wherein R is isopropyl orcyclopropyl; Ar is phenyl optionally substituted with any combination offrom one to three halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy groups; Ar₁ is 3-phenoxyphenyl optionally substitutedwith any combination of from one to six halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy groups; Y is SO₂F orP(O)(OR₁)₂; and R₁ is C₁-C₄-alkyl.
 11. The process according to claim 1for the preparation of1-(p-chlorophenyl)-1-cyclopropyl-2-fluoro-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadiene.12. The process according to claim 1 wherein Y is SO₂F.
 13. The processaccording to claim 1 wherein Y is P(O)(OR₁)₂.
 14. The process accordingto claim 13 wherein R₁ is ethyl.
 15. The process according to claim 1which further comprises a catalytically effective amount of a phasetransfer catalyst.